Amide antioxidants

ABSTRACT

Tertiary amides have been developed which have low volatility and good thermal stability and which are effective in stabilizing organic materials that are normally susceptible to oxidative deterioration. The novel antioxidants are tertiary amides corresponding to the formula: ##STR1## wherein R is a mono-, di-, or trivalent aromatic or saturated aliphatic hydrocarbon group containing 1-20 carbons; n is an integer of 1-3 which is equal to the valence of R; R&#39; is phenyl, benzyl, or C 1  -C 6  alkyl; m is an integer of 1-3; R&#34; is a C 1  -C 4  alkylene group; Z and Z&#39; are independently selected from hydrogen and alkyl; and Q is carbonyl or sulfonyl.

This application is a 371 of PCT/U.S. Ser. No. 92/01559 filed Feb. 26,1992.

FIELD OF INVENTION

This invention relates to novel amides having utility as antioxidants.

BACKGROUND

Many organic materials, such as polymers, fuels, and lubricants, arenormally susceptible to oxidative deterioration and tend to suffersevere degradation and/or discoloration during processing and/or lateruse unless they are stabilized.

The compounds which have previously been proposed for use in stabilizingthese materials have frequently been phenolic compounds, and some suchcompounds have been very successfully employed as antioxidants for someof the normally oxidizable materials. However, no single compound couldbe the best possible antioxidant for each of the variety of organicmaterials which are normally susceptible to oxidative deterioration,since:

(1) the compounds which have the lowest volatility and highest thermalstability are not necessarily those which have the most suitable meltingpoints, the least tendency to degrade to highly-colored compounds, andthe greatest ability to stabilize organic materials during processing,

(2) some of the organic materials (e.g., the polymers) are less capablethan others (e.g., fuels and lubricants) of tolerating the substantialdiscoloration that occurs when many phenolic compounds are subjected toprocessing conditions,

(3) some antioxidant compounds are so volatile and have such poorthermal stability that they are unsuitable for use in organic materialsfor which high processing temperatures and/or long-term stabilizationare required, and

(4) some antioxidant compounds have melting points so high as to presenta drawback to their use in materials which must be processed at low ormoderate temperatures.

Thus, it is necessary to have different antioxidants to serve thedifferent needs of the various organic materials which requirestabilization.

Because of the need for these different antioxidants for differentorganic materials, it would be desirable to be able to find a class ofantioxidants which could be derived from a common intermediate or acommon genus of intermediates that could be easily modified so as toprovide the different antioxidant properties required in the variety ofspecific market needs.

As disclosed in U.S. Pat. Nos. 3,780,103 (Knell), 3,808,273 (Burdet etal.), 3,927,091 (Huber-Emden et al.), 3,996,194 (Gencarelli et al.),4,098,760 (Cornell), 4,100,191 (Fischer et al.), and 4,132,702 (Schmidtet al.) and Netherlands Patent Application 7905000 (Cincinnati MilacronChemicals), it is known that some amides containing substitutedhydroxyphenyl groups have been found to be useful as stabilizers forsome organic materials which are normally susceptible to oxidativedeterioration.

N,N-bis(3,5-di-t-butyl-4-hydroxybenzyl)acetamide is disclosed by G. A.Nikiforov et al. in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya,No. 12, pp. 2765-2770, 1989.

SUMMARY OF INVENTION

The invention resides in (1) tertiary amides corresponding to theformula: ##STR2## wherein R is a mono-, di-, or trivalent aromatic orsaturated aliphatic hydrocarbon group containing 1-20 carbons; n is aninteger of 1-3 which is equal to the valence of R; R' is phenyl, benzyl,or C₁ -C₆ alkyl; m is an integer of 1-3; R" is a C₁ -C₄ alkylene group;Z and Z' are independently selected from hydrogen and alkyl; and Q iscarbonyl or sulfonyl and (2) the use of the tertiary amides asantioxidants for organic materials which are normally susceptible tooxidative deterioration.

DETAILED DESCRIPTION

The novel tertiary amides of the invention are amides containingalkyl-substituted hydroxyphenyl groups which are separated from theamido nitrogens by a linking chain of at least two carbons. This type oflinkage is an important feature of the compounds, since it provideslower volatility and higher thermal stability than a linkage constitutedby a single carbon and thus makes the compounds superior to thecorresponding compounds containing the shorter linkage, e.g., thecompounds of Nikiforov et al.

As indicated by the formula, the p-alkyl substitutent represented byCZZ'R" may have a branched chain when R" is a branched alkylene groupand/or at least one of Z and Z' is alkyl (usually an alkyl of only 1-4carbons). However, it is generally preferred for that substituent to beunbranched except for the branching provided with Z is methyl; and it isapt to be most preferred for the R" alkylene group to be unbranched andfor Z and Z' to be hydrogen so that the CZZ'R" of the formula is a--(CH₂)_(p) group in which p is an integer of 2-5.

As also indicated by the formula, (1) the novel tertiary amides may bederivatives of aliphatic or aromatic carboxamides, diamides, triamides,or the corresponding sulfonamides which provide an R hydrocarbon groupof up to 20 carbons, and (2) the R' substituents on thep-hydroxyphenylalkyl groups may be 1-3 in number; may be phenyl, benzyl,or C₁ -C₆ alkyl; and, when there is more than one, may be the same ordifferent. However, it is usually preferred that there be two suchsubstituents, which are most commonly alkyl groups containing 1-4carbons, in the positions ortho to the hydroxy group.

Exemplary of the novel tertiary amides of the invention are the (1)acetamides, propionamides, isopropionamides, butyramides, palmitamides,stearamides, and benzamides, (2) diamides of malonic, succinic,glutaric, adipic, dodecanoic, tetradecandioic, hexadecandioic,dicarboxycyclohexane, phthalic, isophthalic, and terephthalic acids, (3)triamides of 1,2,3-propanetricarboxylic,2,3-dimethyl-1,2,3-butanetricarboxylic, and 1,2,4- and1,3,5-benzenetricarboxylic acids, and (4) corresponding sulfonamides,such as the methanesulfonamides, propanesulfonamides, andbenzenesulfonamides in which the N-substituents areβ-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl, β-(3-methyl-5-t-butyl-4-hydroxyphenyl)ethyl, β-(3,5-diphenyl-4-hydroxyphenyl)ethyl,β-(3-benzyl-5-methyl-4-hydroxyphenyl)ethyl,β-(3-t-butyl-4-hydroxyphenyl)ethyl,β-(2-methyl-3,5-di-t-butyl-4-hydroxyphenyl)ethyl,β-(3,5-diisopropyl-4-hydroxyphenyl)ethyl,γ-(3,5-di-t-butyl-4-hydroxyphenyl)propyl,γ-(3-methyl-5-t-butyl-4-hydroxyphenyl)propyl,α-methyl-γ-(3,5-di-t-butyl-4-hydroxyphenyl)propyl, orε-(3-t-butyl-4-hydroxyphenyl)pentyl.

Among the more preferred tertiary amides of the invention are (1) theN,N-bis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl ]acetamide,N,N-bis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]stearamide,N,N-bis[β-(3,5-diisopropyl-4-hydroxyphenyl)ethyl]acetamide, andN,N-bis[β-(3-methyl-5-t-butyl-4-hydroxyphenyl)ethyl]acetamidemonoamides, (2) theN,N,N',N'-tetrakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]- andN,N,N',N'-tetrakis[β-(3-methyl-5-t-butyl-4-hydroxyphenyl)ethyl]glutaramide,terephthalamide, succinamide, and adipamide bisamides, (3) theN,N,N',N',N",N"-hexakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]-andN,N,N',N',N",N"-hexakis[β-(3methyl-5-t-butyl-4-hydroxyphenyl)ethyl]-1,3,5-benzenetricarboxamides, and (4) theN,N-bis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]-,N,N-bis[β-(3,5-diisopropyl-4-hydroxyphenyl)ethyl]-, andN,N-bis[β(3-methyl-5-t-butyl-4-hydroxyphenyl)ethyl]methanesulfonamides.

The most preferred of the tertiary amides are apt to beN,N-bis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]acetamide,N,N-bis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]methanesulfonamide,N,N,N',N'-tetrakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]glutaramide,N,N,N',N'-tetrakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]terephthalamide,andN,N,N',N',N",N"-hexakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]-1,3,5-benzenetricarboxamide--theparticular tertiary amide preferred in any specific instance dependingon the needs of the particular organic material being stabilized.

The tertiary amides may be prepared by reacting the appropriate acyl orsulfonyl halide corresponding to the formula R(QX)_(n) with theappropriate secondary amine corresponding to the formula: ##STR3## Xrepresenting halo, preferably chloro or bromo; and R, R', R", Q, Z, Z',m, and n being as previously defined. Thus, for example, (1) an acylhalide such as acetyl chloride, propionyl chloride, butyryl bromide,isobutyryl chloride, stearoyl chloride, or benzoyl chloride, (2) adicarboxylic acid dihalide such as glutaryl dichloride, malonyldichloride, adipyl dibromide, succinyl dichloride, terephthaloyldichloride, isophthaloyl dichloride, cyclopentane-1,3-dicarboxylic aciddibromide, cyclohexane-1,4-dicarboxylic acid dichloride,1,12-dodecanedicarboxylic acid dichloride, or1,14-tetradecanedicarboxylic acid dichloride, (3) a tricarbonyltrihalide such as a 1,2,4- or 1,3,5-benzenetricarbonyl trichloride,1,2,3-propanetricarbonyl tribromide, or2,3-dimethyl-1,2,3-butanetricarbonyl trichloride, or (4) a sulfonylhalide such as methanesulfonyl chloride, 1-butanesulfonyl bromide,1-pentanesulfonyl chloride, 1-decanesulfonyl chloride, orbenzenesulfonyl chloride is reacted with a secondary amine such asbis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]amine,bis[γ-(3-methyl-5-t-butyl4-hydroxyphenyl)propyl]amine, or other suchamine.

In the synthesis of the tertiary amides, the amines and acid halides arereacted in substantially stoichiometric amounts in a solvent which isinert to the reaction and which is capable of solubilizing both thereactants and the product and optionally in the presence of an acidscavenger which can neutralize acid produced by the reaction withoutadversely affecting the process.

Solvents suitable for use in the reaction include, e.g., toluene,benzene, xylene, mesitylene, pentane, hexane, heptane, octane,chlorobenzene, methylene chloride, chloroform, carbon tetrachloride,1,2-dichloroethane, 1,1,2-trichloroethane, diethyl ether, and petroleumether, the preferred solvents usually being toluene and methylenechloride.

Examples of acid scavengers which may be used in the process aretrimethylamine, triethylamine, tripropylamine, tributylamine, pyridine,4-dimethylaminopyridine, and 2,6-lutidine, with the preferred acidscavenger being triethylamine. When employed, the acid scavenger is usedin an amount such as to provide about one mol of acid scavenger per molof acid generated by the reaction.

In the preparation of the tertiary amides, the components of thereaction mixture are combined in any suitable way, conveniently byslowly adding a solution of the amine (and optionally also an acidscavenger) in a portion of the solvent to a solution of the acid halidein the remainder of the solvent while maintaining the reaction mixtureat a temperature of 0°-25° C. Then, when combination of the reactants isat least substantially complete, the temperature is raised, ifnecessary, to be in the range of 10°-45° C., preferably 25°-35° C., andkept in that range for a suitable time, e.g., 2-10 hours. It isordinarily most convenient in this reaction to use ambient temperature.

After completion of the reaction, the product can be recovered in anyappropriate way. For example, the reaction mixture may be diluted withsolvent, preferably the same solvent as was used in the reaction; thediluted reaction mixture may then be washed with an inorganic acid, suchas HCl; the organic phase resulting from this wash may be recovered andwashed with a base, such as NaOH; the organic phase resulting from thiswash may be recovered and washed with a salt solution, e.g., aqueousNaCl; and the organic phase resulting from this wash may be recoveredand dried to yield the desired tertiary amide.

In an embodiment of the invention, the tertiary amides are used asantioxidants for organic materials which are normally susceptible tooxidative deterioration, such as the organic materials taught in Knell,Huber-Emden et al., Gencarelli et al., and Schmidt et al.

Although the organic materials that can be stabilized in the practice ofthe invention include various materials such as fuels, hydrocarbon andester lubricants, plasticizers, epoxy resins, polycarbonates,polyurethanes, polyureas, polyamides, polyesters, polyethers,phenol-formaldehyde resins, urea-formaldehyde resins,melamineformaldehyde resins, and natural polymers (e.g., cellulose,rubber, proteins, and their derivatives), those which are apt to be mostbeneficially stabilized are synthetic polymers such as:

(1) polymers and interpolymers of ethylenically-unsaturatedhydrocarbons, such as ethylene, propylene, butylene, isobutylene,styrene, butadiene, and piperylene, including the homopolymers,copolymers, and other interpolymers thereof with one another, andcopolymers and interpolymers of at least one of them with one or morecopolymerizable non-hydrocarbons, such as vinyl acetate, acrylonitrile,methacrylonitrile, methyl acrylate, and methyl methacrylate,

(2) halogen-containing polymers, such as polyvinyl chloride andfluoride, polyvinylidene chloride, vinyl chloride-vinylidene chloridecopolymers, polychloroprene, and chlorinated rubbers,

(3) other vinyl and allyl polymers, such as polyvinyl alcohol, acetate,stearate, benzoate, maleate, and butyral, polyallylmelamine, andpolyallyl phthalate, and

(4) acrylic polymers, such as polyacrylates, polymethacrylates,polyacrylamides, polyacrylonitrile, and polymethacrylonitrile.

In a particularly preferred embodiment of the invention, the tertiaryamides are used to stabilize thermoplastic polymers, such aspolyethylenes, polypropylenes, and polycarbonates, during processing,e.g., extrusion or injection molding.

The tertiary amides are combined with the normally oxidable materials inantioxidant amounts, usually an amount in the range of 0.005-5%,preferably 0.01-2%, based on the weight of the organic material.

When used as antioxidants, the tertiary amides may be employed as thesole stabilizers for the normally-oxidizable organic materials, or theymay be used in conjunction with other stabilizers, such as conventionalphenolic antioxidants or thioester synergists. Moreover, their activityas antioxidants does not appear to be inhibited by the presence in theorganic materials of additives such as those conventionally employed insuch materials, e.g., light stabilizers, ultraviolet light absorbers,metal deactivators, pigments, dyes, lubricants, nucleating agents, andfillers.

In general, all of the tertiary amides of the invention are goodprocessing stabilizers. However, those having the higher molecularweights--typically also having lower volatility and greater thermalstability--are superior when high processing temperatures and/orlong-term stabilization are required, while those having the lowermolecular weights--typically also having lower melting points--are moresuitable for use when low-to-moderate processing temperatures arerequired.

The following examples are given to illustrate the invention and are notintended as a limitation thereof. Unless otherwise specified, quantitiesmentioned in the examples are quantities by weight. Code names aresometimes used in these examples to identify compounds as shown in TableI.

                                      TABLE I                                     __________________________________________________________________________    Compound                         Code Name                                    __________________________________________________________________________    1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-2,4,6-trimethylben-                                                 E-330                                        zene - a commercially-available antioxidant sold by Ethyl                     Corporation as Ethanox ® 330                                              N,N-bis(3,5-di-t-butyl-4-hydroxybenzyl)acetamide - a com-                                                      N-1190                                       pound taught by Nikiforov et al.                                              N,N-bis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]-2,2,2-trichlo-                                           C-1176                                       roacetamide - a compound taught by Cornell                                    Bis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]amine - a                                                     S-1161nt                                     used in preparing products of the Examples                                    N,N-bis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]acetamide                                                 AN-1162                                      N,N,N',N'-tetrakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]glu-                                           AN-1163                                      taramide                                                                      N,N,N',N'-tetrakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]tere-                                          AN-1164                                      phthalamide                                                                   N,N-bis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]methanesul-                                               AN-1168                                      fonamide                                                                      N,N,N',N',N",N"-hexakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)-                                               AN-1178                                      ethyl]-1,3,5-benzenetricarboxamide                                            __________________________________________________________________________

EXAMPLE 1 Preparation of AN-1162

Charge a suitable reaction vessel with 1.6 g of acetyl chloride and 10mL of dry toluene. While stirring the reaction mixture and maintainingthe temperature at 0°-8° C., slowly add a solution of 9 g of S-1161, 2.1g of triethylamine, and 30 mL of dry toluene. Then allow the reactionmixture to reach ambient temperature and maintain that temperature forfour hours.

After completion of the four-hour period, wash the reaction mixtureconsecutively with 50 mL of 3N HCl, 50 mL of 1N NaOH, and 50 mL of asaturated aqueous NaCl solution, the organic phase being recovered aftereach wash and then subjected to the next wash. Recover the final washedorganic phase, dry, and concentrate in vacuo to provide a 98% yield ofN,N-bis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]acetamide.

Recrystallize the crude product from 100 mL of heptane and wash theprecipitated product with 75 mL of heptane. GC analysis shows therecrystallized product to contain 99% of the tertiary amide, which has amelting point of 153°-155° C. Spectral analyses (H-NMR, ¹³ C-NMR, IR,GC-MS) confirm the identity of the solid asN,N-bis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]acetamide.

EXAMPLE 2 Preparation of AN-1168

Repeat Example 1 except for replacing the acetyl chloride with 2.9 g ofmethanesulfonyl chloride and using 2.7 g of the triethylamine. Prior tothe recrystallization of the crude product from heptane, it contains97.6 area % ofN,N-bis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]methanesulfonamide.After recrystallization, GC analysis shows the product to contain >99%of the tertiary sulfonamide, which has a melting point of 132°-134° C.Spectral analyses (H-NMR, ¹³ C-NMR, IR, GC-MS) confirm the identity ofthe solid asN,N-bis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]methanesulfonamide.

EXAMPLE 3 Preparation of AN-1163

Charge a suitable reaction vessel with 1.78 g of glutaryl dichloride and10 mL of dry toluene. While stirring the reaction mixture andmaintaining the temperature at 0°-8° C., slowly add a solution of 10.1 gof S-1161, 2.31 g of triethylamine, and 30 mL of dry toluene. Then allowthe reaction mixture to reach ambient temperature and maintain thattemperature for four hours.

After completion of the four-hour period, dilute the reaction mixturewith 50 mL of toluene and wash it consecutively with 50 mL of 3N HCl, 50mL of 1N NaOH, and 50 mL of a saturated aqueous NaCl solution, theorganic phase being recovered after each wash and then subjected to thenext wash. Recover the final washed organic phase, dry it, andconcentrate it on a rotary evaporator to provide 11.4 g of product.

Dissolve the product in 350 mL of heptane at 100° C. and recrystallizeit at 0° C. to provide 9.9 g of recrystallized product. TLC analysisshows the recrystallized product to contain 98.1 area % ofN,N,N',N'-tetrakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]glutaramide,which has a melting point of 167°-169° C. The yield is 92%, and spectralanalyses (H-NMR, IR, HRMS, and ¹³ C-NMR) confirm the structure of theproduct.

EXAMPLE 4 Preparation of AN-1164

Repeat the reaction of Example 3 except for replacing the glutaryldichloride with 2.09 g of terephthaloyl dichloride to provide 11.4 g ofproduct. Stir the product in 100 mL of refluxing heptane for one hour,cool to room temperature, and isolate the precipitated product byfiltration. Recrystallize the product from a mixture of 200 mL ofheptane and 160 mL of toluene to provide 9.2 g of recrystallizedproduct. TLC analysis shows this product to contain 99.0 area % ofN,N,N',N'-tetrakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]terephthalamide, which has a melting point of 208°-210° C. The yield is83%, and spectral analyses (H-NMR, IR, HRMS, and ¹³ C-NMR) confirm thestructure of the product.

EXAMPLE 5 Preparation of AN-1178

Slowly add a solution of 10.1 g of S-1161 and 2.3 g of triethylamine in50 mL of dry toluene to a stirred solution of 1.8 g of1,3,5-benzenetricarbonyl trichloride in 15 mL of dry toluene maintainedat 0°-8° C. Then warm the reaction mixture to room temperature and stirovernight to provide 11.7 g of product.

After completing the overnight stir, dilute the reaction mixture with 50mL of toluene and wash it consecutively with 50 mL of 3N HCl, 50 mL of1N NaOH, and 50 mL of a saturated aqueous NaCl solution, the organicphase being recovered after each wash and then subjected to the nextwash. Recover the final washed organic phase, dry it, and concentrate iton a rotary evaporator to provide 11.7 g of product.

Stir the crude product in refluxing heptane for 15 minutes, cool, andisolate the precipitated solids by filtration. Recrystallize theresulting 10.3 g of solids in 100 mL of ethanol and then from a mixtureof 100 mL of heptane and 70 mL of toluene. TLC analysis shows thisproduct to contain 97.5 area % ofN,N,N',N',N",N"-hexakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]-1,3,5-benzenetricarboxamide,which has a melting point of 193°-195° C. The yield is 58%, and spectralanalyses (H-NMR, IR, HRMS, and ¹³ C-NMR) confirm the structure of theproduct.

EXAMPLE 6 Determination of Volatility and Thermal Stability

Subject the products of Examples 1-5 to thermogravimetric analysis byheating different samples of the products at 10° C./minute from 25° C.under nitrogen and air, respectively, to determine the temperatures atwhich there is a 10% weight loss. The results of the analyses are shownin Table II.

                  TABLE II                                                        ______________________________________                                                          °C. in Nitrogen at                                                                   °C. in Air at                          Example Compound  10% Weight Loss                                                                             10% Weight Loss                               ______________________________________                                        1       AN-1162   298           282                                           2       AN-1168   293           293                                           3       AN-1163   359           343                                           4       AN-1164   359           342                                           5       AN-1178   357           348                                           ______________________________________                                    

When N-1190, a compound which has a chain of less than two carbonsbetween the alkyl-substituted hydroxyphenyl groups and the amidonitrogen, is subjected to the same analysis, the analytical results showthe temperatures at which a 10% weight loss is found in nitrogen and airare 245° C. and 249° C., respectively. This demonstrates the lowervolatility and the superior thermal stability of the amides of theinvention.

EXAMPLE 7 Evaluation of Antioxidants in Polypropylene Part A

Prepare two series of polypropylene compositions by (1) blending twodifferent samples of Profax® 6501, a product of Himont Incorporated,with 0.05% of calcium stearate as an acid neutralizer and lubricant, (2)dividing each of these blends into aliquots, and (3) blending each ofthe aliquots to be stabilized with 0.1% of an antioxidant. Theantioxidants used in the blends are:

    ______________________________________                                               Blend Antioxidant                                                      ______________________________________                                               A-1   C-1176                                                                  A-2   N-1190                                                                  A-3   E-330                                                                   A-4   AN-1162                                                                 A-5   AN-1178                                                                 B-1   none                                                                    B-2   E-330                                                                   B-3   AN-1162                                                                 B-4   AN-1163                                                                 B-5   AN-1164                                                                 B-6   AN-1168                                                          ______________________________________                                    

Part B

Test the compositions of Part A for melt flow index and yellowness indexby extruding them in a Brabender twin screw extruder at 150°-245°--245°C. and 30 rpm under nitrogen and then making five passes through aBrabender single screw extruder at 260°--260°--260°--260° C. and 30 rpmwith ambient air. The test results are shown in Table III.

                  TABLE III                                                       ______________________________________                                        MFI @ 230° C./                                                         2160 g Load           Yellowness Index                                        Extrusion Passes      Extrusion Passes                                        Blend  TwS     ss1    ss3   ss5   ss1  ss3   ss5                              ______________________________________                                        A-1    4.7     5.0    6.3   7.4   6.2  10.0  15.0                             A-2    4.7     5.2    6.5   9.0   5.3  6.7   9.3                              A-3    3.7     6.0    10.4  15.5  4.2  5.8   6.8                              A-4    5.2     6.5    9.0   13.2  5.0  6.4   7.9                              A-5    4.8     6.4    11.8  16.3  4.0  5.7   6.9                              B-1    9.6     28.5   96.5  --    3.1  5.8   --                               B-2    4.3     5.9    8.3   10.8  4.9  7.3   10.9                             B-3    4.3     4.9    6.9   8.3   5.5  9.0   12.0                             B-4    4.8     5.8    6.7   8.3   5.9  10.7  15.2                             B-5    4.7     5.7    7.4   9.6   6.0  9.1   12.8                             B-6    4.3     6.1    8.4   10.9  5.5  9.1   12.4                             ______________________________________                                    

Part C

Test the compositions of Part A for resistance to failure on oven agingby (1) molding pellets of the compositions retained from the twin screwpass of Part B into plaques having a thickness of ˜0.06 cm, using ahydraulic press set at 245° C. for the molding, (2) cutting each of theplaques into five ˜2.5 cm squares, (3) placing each of the squares intoglass Petri dishes, (4) placing the Petri dishes into an air-circulatingoven set at 150° C., and (5) checking the samples every 24 hours forfailure--failure being determined when at least three of the fivesquares of a particular composition are visually decomposed. The testresults are shown below.

    ______________________________________                                        Blend      Total Hours @ Failure                                              ______________________________________                                        A-1        120                                                                A-2         48                                                                A-3        384                                                                A-4         96                                                                A-5        576                                                                B-1         24                                                                B-2        336                                                                B-3         96                                                                B-4        864                                                                B-5        840                                                                B-6        120                                                                ______________________________________                                    

As demonstrated in the preceding examples, the tertiary amides of theinvention include a variety of compounds which (1) have utility instabilizing organic materials against deterioration during processingand oven aging, (2) have melting points sufficiently lower than the240°-245° C. melting point of E-330 to make them preferable to thatcommercial antioxidant for use in low-to-moderate temperatureprocessing, (3) have greater thermal stability than amides such asN-1190, and (4) in general, compare favorably with known antioxidants asstabilizers for organic materials which are normally susceptible tooxidative deterioration. Those which have the least tendency towarddeveloping color bodies are particularly valuable for stabilizingorganic materials, such as some of the organic polymers, that are to beused in applications wherein the impartation of color would beundesirable. Those which show greater tendencies to form color are moreapt to be useful in stabilizing organic materials in which color is nota disadvantage, e.g., fuels, lubricants, and some organic polymers.

I claim:
 1. A tertiary amide corresponding to the formula: ##STR4##wherein R is a di or trivalent aromatic or saturated aliphatichydrocarbon group containing 1-20 carbons; n is an integer of 2-3 whichis equal to the valence of R; R' is phenyl, benzyl, or C₁ -C₆ alkyl; mis an integer of 1-3; R" is a C₁ -C₄ alkylene group; Z and Z' areindependently selected from hydrogen and alkyl; and Q is carbonyl. 2.The tertiary amide of claim 1 wherein n is
 2. 3. The tertiary amide ofclaim 2 which is an N,N,N',N'-tetrasubstituted glutaramide wherein R' isan alkyl group of 1-4 carbons, m is 2, and CZZ'R" is (CH₂)_(p) in whichp is an integer of 2-5.
 4. The tertiary amide of claim 3 which isN,N,N',N'-tetrakis[β-(3,5-di-t-butyl-4-hydroxyphenyl) ethyl]glutaramide.5. The tertiary amide of claim 2 which is an N,N,N',N'-tetrasubstitutedterephthalamide wherein R' is an alkyl group of 1-6 carbons, m is 2, andCZZ'R" is (CH₂)_(p) in which p is an integer of 2-5.
 6. The tertiaryamide of claim 5 which isN,N,N',N'-tetrakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]terephthalamide.7. The tertiary amide of claim 1 wherein n is
 3. 8. The tertiary amideof claim 7 which is an N,N,N',N',N",N"-hexasubstituted1,3,5-benzenetricarboxamide wherein R' is an alkyl group of 1-4 carbons,m is 2, and CZZ'R" is (CH₂)_(p) in which p is an integer of 2-5.
 9. Thetertiary amide of claim 8 which isN,N,N',N',N",N"-hexakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl ]-1,3,5-benzenetricarboxamide.
 10. A composition comprising an organic materialselected from the group consisting of a fuel, hydrocarbon lubricant,ester lubricant, plasticizer, synthetic polymer and natural polymer andan antioxidant amount of a tertiary amide corresponding to the formula:##STR5## wherein R is a di- or trivalent aromatic or saturated aliphatichydrocarbon group containing 1-20 carbons, n is an integer of 2 or 3which is equal to the valence of R; R' is phenyl, benzyl, or C₁ -C₆alkyl; m is an integer of 1-3; R" is a C₁ -C₄ alkylene group; Z and Z'are independently selected from hydrogen and alkyl; and Q is carbonyl.11. The composition of claim 10 wherein the organic material which isnormally susceptible to oxidative deterioration is a polymer of anethylenically-unsaturated hydrocarbon.
 12. The composition of claim 11wherein the tertiary amide is an N,N,N',N',N",N"-hexasubstituted1,3,5-benzenetricarboxamide in which R' is an alkyl group of 1-6carbons, m is 2, and CZZ'R" is (CH₂)_(p) in which p is an integer of2-5.
 13. The composition of claim 12 wherein the tertiary amide isN,N,N',N',N",N"-hexakis[β-(3,5-di-t-butyl-4-hydroxyphenyl)ethyl]-1,3,5-benzenetricarboxamide.